U.S. patent application number 11/916233 was filed with the patent office on 2008-09-04 for fungicidal n-benzyl-5-hydroxy-5-phenylpryrazolines, processes for their preparation and compositions comprising them.
Invention is credited to Jochen Dietz, Markus Gewehr, Thomas Grote, Andreas Gypser, Matthias Niedenbruck.
Application Number | 20080214642 11/916233 |
Document ID | / |
Family ID | 36809020 |
Filed Date | 2008-09-04 |
United States Patent
Application |
20080214642 |
Kind Code |
A1 |
Gewehr; Markus ; et
al. |
September 4, 2008 |
Fungicidal N-Benzyl-5-Hydroxy-5-Phenylpryrazolines, Processes For
Their Preparation and Compositions Comprising Them
Abstract
N-benzoyl-5-hydroxy-5-phenylpyrazolines of the formula I
##STR00001## in which the substituents are as defined below:
L.sup.1, L.sup.2 are hydrogen, halogen, haloalkyl, alkenyl,
haloalkenyl, alkynyl or haloalkynyl; L.sup.3, L.sup.4, L.sup.5 are
alkyl or one of the groups mentioned under L.sup.1 and L.sup.2; X
is oxygen or sulfur; R.sup.1 is halogen, nitro, cyano, NR'.sub.2,
alkyl, haloalkyl, alkoxy, alkenyl, haloalkyl, alkynyl, haloalkynyl,
cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl, 5- or 6-membered
heterocyclyl or hetaryl which contains one to four heteroatoms from
the group consisting of O, N and S; R' independently of one another
are hydrogen or alkyl; m is 1, 2, 3, 4 or 5; R.sup.2 is hydrogen or
alkyl; R.sup.3 is hydrogen, nitro, cyano, alkyl, haloalkyl, alkoxy,
haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl or
NR'.sub.2, where R.sup.4 is hydrogen, halogen, nitro, cyano,
NR'.sub.2, alkyl, haloalkyl, COOR' or 5- or 6-membered heterocyclyl
or hetaryl which contains one to four heteroatoms from the group
consisting of O, N and S; where the variables mentioned above may
be substituted according to the description; processes for their
preparation, their use for controlling harmful fungi and
compositions comprising them.
Inventors: |
Gewehr; Markus; (Kastellaun,
DE) ; Dietz; Jochen; (Mannheim, DE) ; Grote;
Thomas; (Wachenheim, DE) ; Gypser; Andreas;
(Mannheim, DE) ; Niedenbruck; Matthias;
(Limburgerhof, DE) |
Correspondence
Address: |
HUTCHISON LAW GROUP PLLC
PO BOX 31686
RALEIGH
NC
27612
US
|
Family ID: |
36809020 |
Appl. No.: |
11/916233 |
Filed: |
May 24, 2006 |
PCT Filed: |
May 24, 2006 |
PCT NO: |
PCT/EP2006/062585 |
371 Date: |
November 30, 2007 |
Current U.S.
Class: |
514/407 ;
548/369.4 |
Current CPC
Class: |
C07D 231/08 20130101;
A01N 43/56 20130101 |
Class at
Publication: |
514/407 ;
548/369.4 |
International
Class: |
A01N 43/56 20060101
A01N043/56; C07D 231/08 20060101 C07D231/08; A01P 3/00 20060101
A01P003/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 31, 2005 |
DE |
10 2005 025 378.4 |
Claims
1-9. (canceled)
10. A compound of formula I, ##STR00008## wherein, L.sup.1, L.sup.2
independently of one another are hydrogen, halogen,
C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkenyl, C.sub.3-C.sub.6-alkynyl or
C.sub.3-C.sub.6-haloalkynyl; L.sup.3, L.sup.4, L.sup.5
independently of one another are C.sub.1-C.sub.6-alkyl or one of
the groups mentioned under L.sup.1 and L.sup.2; provided that at
least one of the groups mentioned above is not hydrogen; X is
oxygen or sulfur; R.sup.1 is halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.6-haloalkynyl; C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkynyl, phenyl,
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; R'
independently of one another are hydrogen or C.sub.1-C.sub.4-alkyl;
m is 1, 2, 3, 4 or 5; R.sup.2 is hydrogen or
C.sub.1-C.sub.10-alkyl; R.sup.3 is hydrogen, nitro, cyano,
NR'.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl,
C.sub.2-C.sub.4-alkynyl or C.sub.2-C.sub.4-haloalkynyl, wherein
R.sup.4 is hydrogen, halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, COOR', phenyl or
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; wherein the
variables mentioned above may be partially or fully halogenated
and/or may carry one to four groups R.sup.a, R.sup.a is halogen,
cyano, nitro, hydroxyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, formyl,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino,
di-C.sub.1-C.sub.6-alkylamino, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-haloalkenyl, C.sub.3-C.sub.8-cycloalkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-haloalkenyloxy,
C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl,
C.sub.3-C.sub.6-alkynyloxy, C.sub.3-C.sub.6-haloalkynyloxy,
C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkenoxy,
C.sub.1-C.sub.3-oxyalkylenoxy, phenyl, naphthyl, a five- to
ten-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S, CR.sup.iii.dbd.NOR.sup.iv, wherein
R.sup.iii is hydrogen, alkyl, cycloalkyl or aryl and R.sup.iv is
alkyl, alkenyl, haloalkenyl, alkynyl or arylalkyl, or
NR.sup.v--CO-D-R.sup.vi, wherein R.sup.v is hydrogen, hydroxyl,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, R.sup.vi is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl or hetaryl-C.sub.1-C.sub.6-alkyl and D is a direct bond,
oxygen or nitrogen, wherein the nitrogen may carry one of the
groups mentioned under R.sup.vi, wherein the aliphatic, alicyclic
or aromatic groups R.sup.a may be partially or fully halogenated or
may carry one to three groups R.sup.b: R.sup.b is halogen, cyano,
nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl,
aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy,
alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino,
dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,
alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,
dialkylaminocarbonyl, alkylaminothiocarbonyl,
dialkylaminothiocarbonyl, wherein the alkyl groups in these
radicals contain 1 to 6 carbon atoms and the alkenyl or alkynyl
groups mentioned in these radicals contain 2 to 8 carbon atoms; one
to three of the following radicals, cycloalkyl, cycloalkoxy,
heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3
to 10 ring members; phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.6-alkoxy, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl, hetaryloxy, hetarylthio, wherein the hetaryl groups
contain 5 or 6 ring members, and the cyclic systems may be
partially or fully halogenated or substituted by alkyl or haloalkyl
groups.
11. The compound of claim 10, wherein said compound has the
following structure I.A, ##STR00009##
12. The compound of claim 11, wherein each of L.sup.1, L.sup.2 and
L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
13. The compound of claim 10, wherein each of L.sup.1, L.sup.2 and
L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
14. A process for preparing a compound of formula I.A ##STR00010##
wherein, L.sup.1, L.sup.2 independently of one another are
hydrogen, halogen, C.sub.1-C.sub.6-haloalkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl,
C.sub.3-C.sub.6-alkynyl or C.sub.3-C.sub.6-haloalkynyl; L.sup.3,
L.sup.4, L.sup.5 independently of one another are
C.sub.1-C.sub.6-alkyl or one of the groups mentioned under L.sup.1
and L.sup.2; provided that at least one of the groups mentioned
above is not hydrogen; R.sup.1 is halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.6-haloalkynyl; C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkynyl, phenyl,
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; R'
independently of one another are hydrogen or C.sub.1-C.sub.4-alkyl;
m is 1, 2, 3, 4 or 5; R.sup.2 is hydrogen or
C.sub.1-C.sub.10-alkyl; R.sup.3 is hydrogen, nitro, cyano,
NR'.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl,
C.sub.2-C.sub.4-alkynyl or C.sub.2-C.sub.4-haloalkynyl, wherein
R.sup.4 is hydrogen, halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, COOR', phenyl or
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; wherein the
variables mentioned above may be partially or fully halogenated
and/or may carry one to four groups R.sup.a, R.sup.a is halogen,
cyano, nitro, hydroxyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, formyl,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino,
di-C.sub.1-C.sub.6-alkylamino, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-haloalkenyl, C.sub.3-C.sub.8-cycloalkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-haloalkenyloxy,
C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl,
C.sub.3-C.sub.6-alkynyloxy, C.sub.3-C.sub.6-haloalkynyloxy,
C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkenoxy,
C.sub.1-C.sub.3-oxyalkylenoxy, phenyl, naphthyl, a five- to
ten-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S, CR.sup.iii.dbd.NOR.sup.iv, wherein
R.sup.iii is hydrogen, alkyl, cycloalkyl or aryl and R.sup.iv is
alkyl, alkenyl, haloalkenyl, alkynyl or arylalkyl, or
NR.sup.v--CO-D-R.sup.vi, wherein R.sup.v is hydrogen, hydroxyl,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, R.sup.vi is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl or hetaryl-C.sub.1-C.sub.6-alkyl and D is a direct bond,
oxygen or nitrogen, wherein the nitrogen may carry one of the
groups mentioned under R.sup.vi, wherein the aliphatic, alicyclic
or aromatic groups R.sup.a may be partially or fully halogenated or
may carry one to three groups R.sup.b: R.sup.b is halogen, cyano,
nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl,
aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy,
alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino,
dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,
alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,
dialkylaminocarbonyl, alkylaminothiocarbonyl,
dialkylaminothiocarbonyl, wherein the alkyl groups in these
radicals contain 1 to 6 carbon atoms and the alkenyl or alkynyl
groups mentioned in these radicals contain 2 to 8 carbon atoms; one
to three of the following radicals, cycloalkyl, cycloalkoxy,
heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3
to 10 ring members; phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.6-alkoxy, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl, hetaryloxy, hetarylthio, wherein the hetaryl groups
contain 5 or 6 ring members, and the cyclic systems may be
partially or fully halogenated or substituted by alkyl or haloalkyl
groups; said method comprising: contacting a compound of formula
II, ##STR00011## wherein L.sup.1, L.sup.2, L.sup.3, L.sup.4 and
R.sup.5 are as defined above with a compound of formula III,
##STR00012## wherein m, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
as defined above, wherein a compound of formula I.A is
prepared.
15. A fungicidal composition comprising a solid or liquid carrier
and a compound of the formula I, ##STR00013## wherein, L.sup.1,
L.sup.2 independently of one another are hydrogen, halogen,
C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkenyl, C.sub.3-C.sub.6-alkynyl or
C.sub.3-C.sub.6-haloalkynyl; L.sup.3, L.sup.4, L.sup.5
independently of one another are C.sub.1-C.sub.6-alkyl or one of
the groups mentioned under L.sup.1 and L.sup.2; provided that at
least one of the groups mentioned above is not hydrogen; X is
oxygen or sulfur; R.sup.1 is halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.6-haloalkynyl; C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkynyl, phenyl,
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; R'
independently of one another are hydrogen or C.sub.1-C.sub.4-alkyl;
m is 1, 2, 3, 4 or 5; R.sup.2 is hydrogen or
C.sub.1-C.sub.10-alkyl; R.sup.3 is hydrogen, nitro, cyano,
NR'.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl,
C.sub.2-C.sub.4-alkynyl or C.sub.2-C.sub.4-haloalkynyl, wherein
R.sup.4 is hydrogen, halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, COOR', phenyl or
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; wherein the
variables mentioned above may be partially or fully halogenated
and/or may carry one to four groups R.sup.a, R.sup.a is halogen,
cyano, nitro, hydroxyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, formyl,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino,
di-C.sub.1-C.sub.6-alkylamino, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-haloalkenyl, C.sub.3-C.sub.8-cycloalkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-haloalkenyloxy,
C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl,
C.sub.3-C.sub.6-alkynyloxy, C.sub.3-C.sub.6-haloalkynyloxy,
C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkenoxy,
C.sub.1-C.sub.3-oxyalkylenoxy, phenyl, naphthyl, a five- to
ten-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S, CR.sup.iii.dbd.NOR.sup.iv, wherein
R.sup.iii is hydrogen, alkyl, cycloalkyl or aryl and R.sup.iv is
alkyl, alkenyl, haloalkenyl, alkynyl or arylalkyl, or
NR.sup.v--CO-D-R.sup.vi, wherein R.sup.v is hydrogen, hydroxyl,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, R.sup.vi is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl or hetaryl-C.sub.1-C.sub.6-alkyl and D is a direct bond,
oxygen or nitrogen, wherein the nitrogen may carry one of the
groups mentioned under R.sup.vi, wherein the aliphatic, alicyclic
or aromatic groups R.sup.a may be partially or fully halogenated or
may carry one to three groups R.sup.b: R.sup.b is halogen, cyano,
nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl,
aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy,
alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino,
dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,
alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,
dialkylaminocarbonyl, alkylaminothiocarbonyl,
dialkylaminothiocarbonyl, wherein the alkyl groups in these
radicals contain 1 to 6 carbon atoms and the alkenyl or alkynyl
groups mentioned in these radicals contain 2 to 8 carbon atoms; one
to three of the following radicals, cycloalkyl, cycloalkoxy,
heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3
to 10 ring members; phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.6-alkoxy, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl, hetaryloxy, hetarylthio, wherein the hetaryl groups
contain 5 or 6 ring members, and the cyclic systems may be
partially or fully halogenated or substituted by alkyl or haloalkyl
groups.
16. The composition of claim 15, wherein said compound has the
following structure I.A, ##STR00014##
17. The composition of claim 16, wherein each of L.sup.1, L.sup.2
and L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
18. The composition of claim 15, wherein each of L.sup.1, L.sup.2
and L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
19. The composition of claim 15, further comprising another active
compound.
20. A seed comprising, a compound of the formula I, ##STR00015##
wherein, L.sup.1, L.sup.2 independently of one another are
hydrogen, halogen, C.sub.1-C.sub.6-haloalkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl,
C.sub.3-C.sub.6-alkynyl or C.sub.3-C.sub.6-haloalkynyl; L.sup.3,
L.sup.4, L.sup.5 independently of one another are
C.sub.1-C.sub.6-alkyl or one of the groups mentioned under L.sup.1
and L.sup.2; provided that at least one of the groups mentioned
above is not hydrogen; X is oxygen or sulfur; R.sup.1 is halogen,
nitro, cyano, NR'.sub.2, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkyl,
C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-haloalkynyl;
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl,
C.sub.3-C.sub.6-cycloalkynyl, phenyl, 5- or 6-membered heterocyclyl
or hetaryl which contains one to four heteroatoms from the group
consisting of O, N and S; R' independently of one another are
hydrogen or C.sub.1-C.sub.4-alkyl; m is 1, 2, 3, 4 or 5; R.sup.2 is
hydrogen or C.sub.1-C.sub.10-alkyl; R.sup.3 is hydrogen, nitro,
cyano, NR'.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl,
C.sub.2-C.sub.4-alkynyl or C.sub.2-C.sub.4-haloalkynyl, wherein
R.sup.4 is hydrogen, halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, COOR', phenyl or
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; wherein the
variables mentioned above may be partially or fully halogenated
and/or may carry one to four groups R.sup.a, R.sup.a is halogen,
cyano, nitro, hydroxyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, formyl,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino,
di-C.sub.1-C.sub.6-alkylamino, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-haloalkenyl, C.sub.3-C.sub.8-cycloalkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-haloalkenyloxy,
C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl,
C.sub.3-C.sub.6-alkynyloxy, C.sub.3-C.sub.6-haloalkynyloxy,
C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkenoxy,
C.sub.1-C.sub.3-oxyalkylenoxy, phenyl, naphthyl, a five- to
ten-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S, CR.sup.iii.dbd.NOR.sup.iv, wherein
R.sup.iii is hydrogen, alkyl, cycloalkyl or aryl and R.sup.iv is
alkyl, alkenyl, haloalkenyl, alkynyl or arylalkyl, or
NR.sup.v--CO-D-R.sup.vi, wherein R.sup.v is hydrogen, hydroxyl,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, R.sup.vi is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl or hetaryl-C.sub.1-C.sub.6-alkyl and D is a direct bond,
oxygen or nitrogen, wherein the nitrogen may carry one of the
groups mentioned under R.sup.vi, wherein the aliphatic, alicyclic
or aromatic groups R.sup.a may be partially or fully halogenated or
may carry one to three groups R.sup.b: R.sup.b is halogen, cyano,
nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl,
aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy,
alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino,
dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,
alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,
dialkylaminocarbonyl, alkylaminothiocarbonyl,
dialkylaminothiocarbonyl, wherein the alkyl groups in these
radicals contain 1 to 6 carbon atoms and the alkenyl or alkynyl
groups mentioned in these radicals contain 2 to 8 carbon atoms; one
to three of the following radicals, cycloalkyl, cycloalkoxy,
heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3
to 10 ring members; phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.6-alkoxy, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl, hetaryloxy, hetarylthio, wherein the hetaryl groups
contain 5 or 6 ring members, and the cyclic systems may be
partially or fully halogenated or substituted by alkyl or haloalkyl
groups said compound being present in an amount of from 1 to 1000 g
per 100 kg seed.
21. The seed of claim 20, wherein said compound has the following
structure I.A, ##STR00016##
22. The seed of claim 21, wherein each of L.sup.1, L.sup.2 and
L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
23. The seed of claim 20, wherein each of L.sup.1, L.sup.2 and
L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
24. A method for controlling phytopathogenic harmful fungi
comprising, treating the fungi or the materials, plants, the soil
or seed to be protected from fungal attack with an effective amount
of a compound of formula I, ##STR00017## wherein, L.sup.1, L.sup.2
independently of one another are hydrogen, halogen,
C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkenyl, C.sub.3-C.sub.6-alkynyl or
C.sub.3-C.sub.6-haloalkynyl; L.sup.3, L.sup.4, L.sup.5
independently of one another are C.sub.1-C.sub.6-alkyl or one of
the groups L.sup.1 and L.sup.2; provided that at least one of the
groups mentioned above is not hydrogen; X is oxygen or sulfur;
R.sup.1 is halogen, nitro, cyano, NR'.sub.2, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkyl,
C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-haloalkynyl;
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl,
C.sub.3-C.sub.6-cycloalkynyl, phenyl, 5- or 6-membered heterocyclyl
or hetaryl which contains one to four heteroatoms from the group
consisting of O, N and S; R' independently of one another are
hydrogen or C.sub.1-C.sub.4-alkyl; m is 1, 2, 3, 4 or 5; R.sup.2 is
hydrogen or C.sub.1-C.sub.10-alkyl; R.sup.3 is hydrogen, nitro,
cyano, NR'.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl,
C.sub.2-C.sub.4-alkynyl or C.sub.2-C.sub.4-haloalkynyl, wherein
R.sup.4 is hydrogen, halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, COOR', phenyl or
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; wherein the
variables mentioned above may be partially or fully halogenated
and/or may carry one to four groups R.sup.a, R.sup.a is halogen,
cyano, nitro, hydroxyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, formyl,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino,
di-C.sub.1-C.sub.6-alkylamino, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-haloalkenyl, C.sub.3-C.sub.8-cycloalkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-haloalkenyloxy,
C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl,
C.sub.3-C.sub.6-alkynyloxy, C.sub.3-C.sub.6-haloalkynyloxy,
C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkenoxy,
C.sub.1-C.sub.3-oxyalkylenoxy, phenyl, naphthyl, a five- to
ten-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S, CR.sup.iii.dbd.NOR.sup.iv, wherein
R.sup.iii is hydrogen, alkyl, cycloalkyl or aryl and R.sup.iv is
alkyl, alkenyl, haloalkenyl, alkynyl or arylalkyl, or
NR.sup.v--CO-D-R.sup.vi, wherein R.sup.v is hydrogen, hydroxyl,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, R.sup.vi is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl or hetaryl-C.sub.1-C.sub.6-alkyl and D is a direct bond,
oxygen or nitrogen, wherein the nitrogen may carry one of the
groups mentioned under R.sup.vi, wherein the aliphatic, alicyclic
or aromatic groups R.sup.a may be partially or fully halogenated or
may carry one to three groups R.sup.b: R.sup.b is halogen, cyano,
nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl,
aminothiocarbonyl, alkyl, haloalkyl, alkenyl, alkenyloxy,
alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino,
dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,
alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,
dialkylaminocarbonyl, alkylaminothiocarbonyl,
dialkylaminothiocarbonyl, wherein the alkyl groups in these
radicals contain 1 to 6 carbon atoms and the alkenyl or alkynyl
groups mentioned in these radicals contain 2 to 8 carbon atoms; one
to three of the following radicals, cycloalkyl, cycloalkoxy,
heterocyclyl, heterocyclyloxy, wherein the cyclic systems contain 3
to 10 ring members; phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.6-alkoxy, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl, hetaryloxy, hetarylthio, wherein the hetaryl groups
contain 5 or 6 ring members, and the cyclic systems may be
partially or fully halogenated or substituted by alkyl or haloalkyl
groups, wherein said phytopathogenic harmful fungi is
controlled.
25. The method of claim 24, wherein said compound has the following
structure I.A, ##STR00018##
26. The method of claim 25, wherein each of L.sup.1, L.sup.2 and
L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
27. The method of claim 24, wherein each of L.sup.1, L.sup.2 and
L.sup.3 is hydrogen and L.sup.4 is other than hydrogen.
Description
[0001] The present invention relates to
N-benzyl-5-hydroxy-5-phenylpyrazolines of the formula I
##STR00002##
in which the substituents are as defined below: [0002] L.sup.1,
L.sup.2 independently of one another are hydrogen, halogen,
C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkenyl, C.sub.3-C.sub.6-alkynyl or
C.sub.3-C.sub.6-haloalkynyl; [0003] L.sup.3, L.sup.4, L.sup.5
independently of one another are C.sub.1-C.sub.6-alkyl or one of
the groups mentioned under L.sup.1 and L.sup.2; [0004] where at
least one of the groups mentioned above is not hydrogen; [0005] X
is oxygen or sulfur; [0006] R.sup.1 is halogen, nitro, cyano,
NR'.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-haloalkyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.6-haloalkynyl; C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkynyl, phenyl,
5- or 6-membered heterocyclyl or hetaryl which contains one to four
heteroatoms from the group consisting of O, N and S; [0007] R'
independently of one another are hydrogen or C.sub.1-C.sub.4-alkyl;
[0008] m is 1, 2, 3, 4 or 5; [0009] R.sup.2 is hydrogen or
C.sub.1-C.sub.10-alkyl; [0010] R.sup.3 is hydrogen, nitro, cyano,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl or NR'.sub.2;
[0011] R.sup.4 is hydrogen, halogen, nitro, cyano, NR'.sub.2,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, COOR', phenyl or
5- or 6-membered hetaryl or heterocyclyl which contains one to four
heteroatoms from the group consisting of O, N and S; where the
variables mentioned above may be partially or fully halogenated
and/or may carry one to four groups R.sup.a, [0012] R.sup.a is
halogen, cyano, nitro, hydroxyl, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, formyl,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino,
di-C.sub.1-C.sub.6-alkylamino, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.8-haloalkenyl, C.sub.3-C.sub.6-cycloalkenyl,
C.sub.2-C.sub.6-alkenyloxy, C.sub.3-C.sub.6-haloalkenyloxy,
C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl,
C.sub.3-C.sub.6-alkynyloxy, C.sub.3-C.sub.6-haloalkynyloxy,
C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkenoxy,
C.sub.1-C.sub.3-oxyalkylenoxy, phenyl, naphthyl, a five- to
ten-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S, CR.sup.iii.dbd.NOR.sup.iv, where [0013]
R.sup.iii is hydrogen, alkyl, cycloalkyl or aryl and [0014]
R.sup.iv is alkyl, alkenyl, haloalkenyl, alkynyl or arylalkyl, or
[0015] NR.sup.v--CO-D-R.sup.vi, where [0016] R.sup.v is hydrogen,
hydroxyl, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, [0017] R.sup.vi is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkenyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl or hetaryl-C.sub.1-C.sub.6-alkyl and D is a direct bond,
oxygen or nitrogen, where the nitrogen may carry one of the groups
mentioned under R.sup.vi, [0018] where the aliphatic, alicyclic or
aromatic groups R.sup.a for their part may be partially or fully
halogenated or may carry one to three groups R.sup.b: [0019]
R.sup.b is halogen, cyano, nitro, hydroxyl, mercapto, amino,
carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl,
alkenyl, alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio,
alkylamino, dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl,
alkylsulfoxyl, alkoxycarbonyl, alkylcarbonyloxy,
alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl,
dialkylaminothiocarbonyl, where the alkyl groups in these radicals
contain 1 to 6 carbon atoms and the alkenyl or alkynyl groups
mentioned in these radicals contain 2 to 8 carbon atoms; [0020]
and/or one to three of the following radicals: [0021] cycloalkyl,
cycloalkoxy, heterocyclyl, heterocyclyloxy, where the cyclic
systems contain 3 to 10 ring members; phenyl, phenoxy, phenylthio,
phenyl-C.sub.1-C.sub.6-alkoxy, phenyl-C.sub.1-C.sub.6-alkyl,
hetaryl, hetaryloxy, hetarylthio, where the hetaryl groups contain
5 or 6 ring members, and the cyclic systems may be partially or
fully halogenated or substituted by alkyl or haloalkyl groups.
[0022] Moreover, the invention relates to processes for their
preparation, to their use for controlling harmful fungi and to
compositions comprising them.
[0023] Substituted pyrazolin-5-ones having herbicidal and
fungicidal activity are known from DE-A 37 28 278, fungicidally
active 3-arylpyrazoles are disclosed in WO-A 94/29276 and WO
00/20399.
[0024] However, in many cases their activity is unsatisfactory.
Accordingly, it was an object of the present invention to provide
compounds having improved activity.
[0025] We have found that this object is achieved by the novel
5-hydroxypyrazoles of the formula I. The novel compounds differ
from those known from WO 00/20399 essentially by the substitution
of the phenyl groups.
[0026] Compounds of the formula I are present in a tautomeric
equilibrium with the open-chain form Ia [cf.: J. Org. Chem. USSR
(1983), 2037; ibid. (1984), 1247].
[0027] The invention therefore relates to both forms, even if, for
the sake of clarity, only the ring form I is mentioned in each
case.
##STR00003##
[0028] Compounds of the formula I in which X is oxygen (formula
I.A) can be obtained, for example, by the following route:
##STR00004##
[0029] This reaction is usually carried out at from 0.degree. C. to
200.degree. C., preferably from 20.degree. C. to 100.degree. C., in
an inert organic solvent [J. Org. Chem. USSR (Engl. Transl.), 16
(1980), 371; ibid. 21 (1985), 2279; ibid. 22 (1986), 250; ibid. 23
(1987), 1291; Indian J. Chem. Sect. B, 29 (1990), 887; Bull. Soc.
Chem. Jp. 62 (1989), 3409].
[0030] Suitable solvents are aliphatic hydrocarbons, aromatic
hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated
hydrocarbons, such as methylene chloride, chloroform and
chlorobenzene, ethers, such as diethyl ether, diisopropyl ether,
tert-butyl methyl ether, dioxane and tetrahydrofuran, nitriles,
such as acetonitrile and propionitrile, alcohols, such as methanol,
ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and
also dimethyl sulfoxide, dimethylformamide and dimethylacetamide,
particularly preferably methanol, ethanol and tetrahydrofuran. It
is also possible to use mixtures of the abovementioned
solvents.
[0031] The starting materials are generally reacted with one
another in equimolar amounts. In terms of yield, it may be
advantageous to employ an excess of III, based on II.
[0032] The hydrazides of the formula II required for preparing the
compounds I are known from the literature [cf. J. Heterocycl. Chem.
16 (1976), 561; Helv. Chim. Acta, 27 (1944), 883; J. Chem. Soc.
(1943), 413], or they can be prepared in accordance with the
literature cited.
[0033] Hydrazides of the formula II are usually prepared from the
corresponding benzoic esters of the formula V by reaction with
hydrazine hydrate. In the formula V, R' is
C.sub.1-C.sub.4-alkyl.
##STR00005##
[0034] This reaction is usually carried out at from 0.degree. C. to
150.degree. C., preferably from 20.degree. C. to 100.degree. C., in
an inert organic solvent [cf. J. Heterocycl. Chem. 16 (1976), 561;
Helv. Chim. Acta, 27 (1944), 883; J. Chem. Soc. (1943), 413].
[0035] The diketones of the formula III required for preparing the
compounds I are also known from the literature [Organikum, VEB
Verlag der Wissenschaften, 15th ed. p. 584ff., Berlin 1976], or
they can be prepared in accordance with the literature cited.
[0036] The compounds of the formula I in which X is sulfur (formula
I.B) can be obtained from the corresponding compounds of the
formula I.A by reaction with a sulfurizing agent.
##STR00006##
[0037] The sulfurization of I.A is carried out under conditions
known per se, usually at from 0.degree. C. to 180.degree. C.,
preferably from 20.degree. C. to 140.degree. C., in an inert
organic solvent [cf. Liebigs Ann. Chem., (1989), 177].
[0038] Suitable solvents are aliphatic hydrocarbons, such as
pentane, hexane, cyclohexane and petroleum ether, aromatic
hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated
hydrocarbons, such as methylene chloride, chloroform and
chlorobenzene, ethers, such as diethyl ether, diisopropyl ether,
tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran,
nitriles, such as acetonitrile and propionitrile, and also dimethyl
sulfoxide, particularly preferably toluene and tetrahydrofuran. It
is also possible to employ mixtures of the abovementioned
solvents.
[0039] Suitable sulfurizing agents are, for example, phosphorus
pentasulfide or Lawesson's reagent.
[0040] The reaction mixtures are worked up in a customary manner,
for example by mixing with water, phase separation and, if
appropriate, chromatographic purification of the crude products.
Some of the intermediates and end products are obtained in the form
of colorless or slightly brownish, viscous oils, which are purified
or freed from volatile components under reduced pressure and at
moderately elevated temperature. If the intermediates and end
products are obtained as solids, purification can also be carried
out by recrystallization or digestion.
[0041] In the definitions of the symbols given in the above
formulae, collective terms were used which generally represent the
following substituents:
halogen: fluorine, chlorine, bromine and iodine; alkyl: saturated,
straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8
or 10 carbon atoms, for example C.sub.1-C.sub.6-alkyl such as
methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,
2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl,
2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,
hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl:
straight-chain or branched alkyl groups having 1 to 10 carbon atoms
(as mentioned above), where the hydrogen atoms in these groups may
be partially or fully replaced by halogen atoms as mentioned above,
for example C.sub.1-C.sub.2-haloalkyl such as chloromethyl,
bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,
difluoromethyl, trifluoromethyl, chlorofluoromethyl,
dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,
1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,
2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
2,2,2-trichloroethyl and pentafluoroethyl; alkenyl: unsaturated,
straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8
or 10 carbon atoms and a double bond in any position, for example
C.sub.2-C.sub.6-alkenyl such as ethenyl, 1-propenyl, 2-propenyl,
1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,
1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,
2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,
4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,
3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,
1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and
1-ethyl-2-methyl-2-propenyl; haloalkenyl: unsaturated,
straight-chain or branched hydrocarbon radicals having 2 to 10
carbon atoms and a double bond in any position (as mentioned
above), where the hydrogen atoms in these groups may be partially
or fully replaced by halogen atoms as mentioned above, in
particular by fluorine, chlorine and bromine; alkynyl:
straight-chain or branched hydrocarbon groups having 2 to 4, 6, 8
or 10 carbon atoms and a triple bond in any position, for example
C.sub.2-C.sub.6-alkynyl such as ethynyl, 1-propynyl, 2-propynyl,
1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,
2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,
1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,
1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,
3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,
1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,
2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,
4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,
1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,
2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,
1-ethyl-3-butynyl, 2-ethyl-3-butynyl and
1-ethyl-1-methyl-2-propynyl; haloalkynyl: unsaturated,
straight-chain or branched hydrocarbon radicals having 2 to 10
carbon atoms and a triple bond in any position (as mentioned
above), where the hydrogen atoms in these groups may be partially
or fully replaced by halogen atoms as mentioned above, in
particular fluorine, chlorine and bromine; cycloalkyl: monocyclic,
saturated hydrocarbon groups having 3 to 6, 8, 10 or 12 carbon ring
members, for example C.sub.3-C.sub.8-cycloalkyl such as
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and
cyclooctyl; heterocyclyl: 5- or 6-membered heterocycles containing,
in addition to carbon ring members, one to three nitrogen atoms
and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur
atoms, for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl,
2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl,
3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl,
5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl,
5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl,
2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl,
2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,
1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,
1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,
1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,
1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl,
2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl,
2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl,
2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl,
3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl,
3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl,
3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl,
3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl,
3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl,
3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl,
3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl,
2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl,
2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl,
3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl,
3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl,
4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl,
4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl,
2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl,
2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl,
3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,
3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl,
3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,
3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl,
4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl,
4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl,
4-hexahydropyridazinyl, 2-hexahydropyrimidinyl,
4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl,
1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;
hetaryl: [0042] 5-membered hetaryl containing one to four nitrogen
atoms or one to three nitrogen atoms and one sulfur or oxygen atom:
hetaryl groups having 5 ring members which, in addition to carbon
atoms, may contain one to four nitrogen atoms or one to three
nitrogen atoms and one sulfur or oxygen atom as ring members, for
example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl,
3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl,
3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl,
4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl,
2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,
1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,
1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl,
1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl; [0043] benzo-fused
5-membered hetaryl containing one to three nitrogen atoms or one
nitrogen atom and one oxygen or sulfur atom: hetaryl groups having
5 ring members which, in addition to carbon atoms, may contain one
to four nitrogen atoms or one to three nitrogen atoms and one
sulfur or oxygen atom as ring members and in which two adjacent
carbon ring members or one nitrogen and one adjacent carbon ring
member may be bridged by a buta-1,3-diene-1,4-diyl group; [0044]
5-membered hetaryl which is linked via nitrogen and contains one to
four nitrogen atoms, or benzo-fused 5-membered hetaryl which is
linked via nitrogen and contains one to three nitrogen atoms:
hetaryl groups having 5 ring members which, in addition to carbon
atoms, may contain one to four nitrogen atoms or one to three
nitrogen atoms as ring members and in which two adjacent carbon
ring members or one nitrogen and one adjacent carbon ring member
may be bridged by a buta-1,3-diene-1,4-diyl group, these rings
being linked to the skeleton via one of the nitrogen ring members;
[0045] 6-membered hetaryl containing one to three or one to four
nitrogen atoms: hetaryl groups having 6 ring members which, in
addition to carbon atoms, may contain one to three or one to four
nitrogen atoms as ring members, for example 2-pyridinyl,
3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,
2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,
1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.
[0046] In general, the alkyl groups in the various substituents
preferably have 1 to 6 carbon atoms, in particular 1 to 4 carbon
atoms, and the alkenyl or alkynyl groups mentioned contain 2 to 8
carbon atoms.
[0047] With respect to the intended use of the 5-hydroxypyrazolines
of the formula I, particular preference is given to the following
meanings of the substituents, in each case both on their own or in
combination:
[0048] Compounds I.A are a preferred embodiment.
##STR00007##
[0049] In addition, particular preference is given to compounds I
in which L.sup.1 and L.sup.2 are hydrogen or halogen.
[0050] A further preferred embodiment of the compounds I relates to
those where L.sup.1, L.sup.2 and L.sup.4 are hydrogen and L.sup.3
is not hydrogen.
[0051] A further preferred embodiment of the compounds I relates to
those where L.sup.1, L.sup.2 and L.sup.3 are hydrogen and L.sup.4
is not hydrogen.
[0052] Particular preference is given to compounds I in which
R.sup.1.sub.m is a substituent in the para position.
[0053] Special preference is also given to compounds I in which
R.sup.1 is halogen or C.sub.1-C.sub.4-alkyl.
[0054] Compounds of the formula I in which R.sup.2 is hydrogen or
C.sub.1-C.sub.4-alkyl, in particular hydrogen, are a preferred
subject matter of the invention.
[0055] Furthermore, particular preference is given to compounds I
in which R.sup.3 is hydrogen.
[0056] Moreover, particular preference is given to compounds I in
which R.sup.4 is hydrogen or methyl.
[0057] Particular preference is likewise given to compounds I in
which R.sup.4 is trifluoromethyl.
[0058] Special preference is also given to compounds I in which
R.sup.4 is cyano, C.sub.2-C.sub.4-alkyl or
C.sub.2-C.sub.4-haloalkyl.
[0059] With respect to their use, particular preference is given to
the compounds I compiled in the tables below. Moreover, the groups
mentioned for a substituent in the tables are, by themselves and
independently of the combination in which they are mentioned, a
particularly preferred embodiment of the substituent in
question.
Table 1
[0060] Compounds of the formula I.A in which R.sup.1.sub.m is
4-chloro, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 is methyl and
the combination of L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5
for a compound corresponds in each case to one row of Table A
Table 2
[0061] Compounds of the formula I.A in which R.sup.1.sub.m is
4-chloro, R.sup.3 is hydrogen, R.sup.2 and R.sup.4 are methyl and
the combination of L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5
for a compound corresponds in each case to one row of Table A
Table 3
[0062] Compounds of the formula I.A in which R.sup.1.sub.m is
4-chloro, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 is
trifluoromethyl and the combination of L.sup.1, L.sup.2, L.sup.3,
L.sup.4 and L.sup.5 for a compound corresponds in each case to one
row of Table A
Table 4
[0063] Compounds of the formula I.A in which R.sup.1.sub.m is
4-chloro, R.sup.2 is hydrogen, R.sup.3 is methyl, R.sup.4 is
trifluoromethyl and the combination of L.sup.1, L.sup.2, L.sup.3,
L.sup.4 and L.sup.5 for a compound corresponds in each case to one
row of Table A
Table 5
[0064] Compounds of the formula I.A in which R.sup.1.sub.m is
4-fluoro, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 is methyl and
the combination of L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5
for a compound corresponds in each case to one row of Table A
Table 6
[0065] Compounds of the formula I.A in which R.sup.1.sub.m is
4-fluoro, R.sup.3 is hydrogen, R.sup.2 and R.sup.4 are methyl and
the combination of L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5
for a compound corresponds in each case to one row of Table A
Table 7
[0066] Compounds of the formula I.A in which R.sup.1.sub.m is
4-fluoro, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 is
trifluoromethyl and the combination of L.sup.1, L.sup.2, L.sup.3,
L.sup.4 and L.sup.5 for a compound corresponds in each case to one
row of Table A
Table 8
[0067] Compounds of the formula I.A in which R.sup.1.sub.m is
4-fluoro, R.sup.2 is hydrogen, R.sup.3 is methyl, R.sup.4 is
trifluoromethyl and the combination of L.sup.1, L.sup.2, L.sup.3,
L.sup.4 and L.sup.5 for a compound corresponds in each case to one
row of Table A
Table 9
[0068] Compounds of the formula I.A in which R.sup.1.sub.m is
4-methyl, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 is methyl and
the combination of L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5
for a compound corresponds in each case to one row of Table A
Table 10
[0069] Compounds of the formula I.A in which R.sup.1.sub.m is
4-methyl, R.sup.3 is hydrogen, R.sup.2 and R.sup.4 are methyl and
the combination of L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5
for a compound corresponds in each case to one row of Table A
Table 11
[0070] Compounds of the formula I.A in which R.sup.1.sub.m is
4-methyl, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 is
trifluoromethyl and the combination of L.sup.1, L.sup.2, L.sup.3,
L.sup.4 and L.sup.5 for a compound corresponds in each case to one
row of Table A
Table 12
[0071] Compounds of the formula I.A in which R.sup.1.sub.m is
4-methyl, R.sup.2 is hydrogen, R.sup.3 is methyl, R.sup.4 is
trifluoromethyl and the combination of L.sup.1, L.sup.2, L.sup.3,
L.sup.4 and L.sup.5 for a compound corresponds in each case to one
row of Table A
TABLE-US-00001 TABLE A No. L.sup.1 L.sup.2 L.sup.3 L.sup.4 L.sup.5
A-1 F H H H H A-2 H H F H H A-3 H H H F H A-4 Cl H H H H A-5 H H Cl
H H A-6 H H H Cl H A-7 Br H H H H A-8 H H Br H H A-9 H H H Br H
A-10 CH.sub.3 H H H H A-11 H H CH.sub.3 H H A-12 H H H CH.sub.3 H
A-13 CH.sub.2CH.sub.3 H H H H A-14 H H CH.sub.2CH.sub.3 H H A-15 H
H H CH.sub.2CH.sub.3 H A-16 F H H F H A-17 H H F F H A-18 H H F H F
A-19 Cl H H Cl H A-20 H H Cl Cl H A-21 H H Cl H Cl A-22 Br H H Br H
A-23 H H Br Br H A-24 H H Br H Br A-25 F H H Cl H A-26 H H F Cl H
A-27 H H F H Cl A-28 F H H Br H A-29 H H F Br H A-30 H H F H Br
A-31 Cl H H F H A-32 H H Cl F H A-33 Cl H H Br H A-34 H H Cl Br H
A-35 H H Cl H Br A-36 Br H H F H A-37 H H Br F H A-38 Br H H Cl H
A-39 H H Br Cl H
[0072] The compounds I are suitable as fungicides. They are
distinguished by an outstanding effectiveness against a broad
spectrum of phytopathogenic fungi from the classes of the
Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some are
systemically effective and they can be used in plant protection as
foliar fungicides, as fungicides for seed dressing and as soil
fungicides.
[0073] They are particularly important in the control of a
multitude of fungi on various cultivated plants, such as wheat,
rye, barley, oats, rice, maize, grass, bananas, cotton, soya,
coffee, sugar cane, vines, fruits and ornamental plants, and
vegetables, such as cucumbers, beans, tomatoes, potatoes and
cucurbits, and on the seeds of these plants.
[0074] They are especially suitable for controlling the following
plant diseases: [0075] Alternaria species on vegetables, oilseed
rape, sugar beet and fruit and rice, such as, for example, A.
solani or A. alternata on potatoes and tomatoes, [0076] Aphanomyces
species on sugar beet and vegetables, [0077] Ascochyta species on
cereals and vegetables, [0078] Bipolaris and Drechslera species on
corn, cereals, rice and lawns, such as, for example, D. maydis on
corn, [0079] Blumeria graminis (powdery mildew) on cereals, [0080]
Botrytis cinerea (gray mold) on strawberries, vegetables, flowers
and grapevines, [0081] Bremia lactucae on lettuce, [0082]
Cercospora species on corn, soybeans, rice and sugar beet, [0083]
Cochliobolus species on corn, cereals, rice, such as, for example
Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice,
[0084] Colletotricum species on soybeans and cotton, [0085]
Drechslera species, Pyrenophora species on corn, cereals, rice and
lawns, such as, for example, D. teres on barley or D.
tritici-repentis on wheat, [0086] Esca on grapevines, caused by
Phaeoacremonium chlamydosporium, Ph. Aleophilum and Formitipora
punctata (syn. Phellinus punctatus), [0087] Exserohilum species on
corn, [0088] Erysiphe cichoracearum and Sphaerotheca fuliginea on
cucumbers; [0089] Fusarium and Verticillium species on various
plants, such as, for example, F graminearum or F. culmorum on
cereals or F. oxysporum on a multitude of plants, such as, for
example, tomatoes, [0090] Gaeumanomyces graminis on cereals, [0091]
Gibberella species on cereals and rice (for example Gibberella
fujikuroi on rice), [0092] Grainstaining complex on rice, [0093]
Helminthosporium species on corn and rice, [0094] Michrodochium
nivale on cereals, [0095] Mycosphaerella species on cereals,
bananas and groundnuts, such as, for example, M. graminicola on
wheat or M. fijiensis on bananas, [0096] Peronospora species on
cabbage and bulbous plants, such as, for example, P. brassicae on
cabbage or P. destructor on onions, [0097] Phakopsara pachyrhizi
and Phakopsara meibomiae on soybeans, [0098] Phomopsis species on
soybeans and sunflowers, [0099] Phytophthora infestans on potatoes
and tomatoes, [0100] Phytophthora species on various plants, such
as, for example, P. capsici on bell pepper, [0101] Plasmopara
viticola on grapevines, [0102] Podosphaera leucotricha on apples,
[0103] Pseudocercosporella herpotrichoides on cereals, [0104]
Pseudoperonospora on various plants, such as, for example, P.
cubensis on cucumber or P. humili on hops, [0105] Puccinia species
on various plants, such as, for example, P. triticina, P.
striformins, P. hordei or P. graminis on cereals or P. asparagi on
asparagus, [0106] Pyricularia oryzae, Corticium sasakii,
Sarocladium oryzae, S. attenuatum, Entyloma oryzae on rice, [0107]
Pyricularia grisea on lawns and cereals, [0108] Pythium spp. on
lawns, rice, corn, cotton, oilseed rape, sunflowers, sugar beet,
vegetables and other plants, such as, for example, P. ultiumum on
various plants, P. aphanidermatum on lawns, [0109] Rhizoctonia
species on cotton, rice, potatoes, lawns, corn, oilseed rape,
potatoes, sugar beet, vegetables and on various plants, such as,
for example, R. solani on beet and various plants, [0110]
Rhynchosporium secalis on barley, rye and triticale, [0111]
Sclerotinia species on oilseed rape and sunflowers, [0112] Septoria
tritici and Stagonospora nodorum on wheat, [0113] Erysiphe (syn.
Uncinula) necator on grapevines, [0114] Setospaeria species on corn
and lawns, [0115] Sphacelotheca reilinia on corn, [0116]
Thievaliopsis species on soybeans and cotton, [0117] Tilletia
species on cereals, [0118] Ustilago species on cereals, corn and
sugar cane, such as, for example, U. maydis on corn, [0119]
Venturia species (scab) on apples and pears, such as, for example,
V. inaequalis on apples.
[0120] They are particularly suitable for controlling harmful fungi
from the class of the Peronosporomycetes (syn. Oomycetes) such as
Peronospora species, Phytophthora species, Plasmopara viticola,
Pseudoperonospora species and Pythium species.
[0121] The compounds I are also suitable for controlling harmful
fungi in the protection of materials (for example wood, paper,
paint dispersions, fibers or fabrics) and in the protection of
stored products. In the protection of wood, particular attention is
paid to the following harmful fungi:
Ascomycetes, such as Ophiostoma spp., Ceratocystis spp.,
Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp.,
Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such
as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus
spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp.,
Deuteromycetes, such as Aspergillus spp., Cladosporium spp.,
Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces
spp. and Zygomycetes, such as Mucor spp., additionally in the
protection of materials the following yeasts: Candida spp. and
Saccharomyces cerevisae.
[0122] The compounds I are employed by treating the fungi or the
plants, seeds, materials or the soil to be protected from fungal
attack with a fungicidally effective amount of the active
compounds. The application can be carried out both before and after
the infection of the materials, plants or seeds by the fungi.
[0123] The fungicidal compositions generally comprise between 0.1
and 95%, preferably between 0.5 and 90%, by weight of active
compound.
[0124] When employed in plant protection, the amounts applied are,
depending on the kind of effect desired, between 0.01 and 2.0 kg of
active compound per ha.
[0125] In seed treatment, amounts of active compound of from 1 to
1000 g/100 kg, preferably from 5 to 100 g/100 kg, of seed are
generally necessary.
[0126] When used in the protection of materials or stored products,
the amount of active compound applied depends on the kind of
application area and on the desired effect. Amounts customarily
applied in the protection of materials are, for example, 0.001 g to
2 kg, preferably 0.005 g to 1 kg, of active compound per cubic
meter of treated material.
[0127] The compounds of the formula I may be present in various
crystal modifications whose biological activities may differ. They
are likewise provided by the present invention.
[0128] The compounds I can be converted into the customary
formulations, for example solutions, emulsions, suspensions, dusts,
powders, pastes and granules. The use form depends on the
particular intended use; it should in each case ensure a fine and
uniform distribution of the compound according to the
invention.
[0129] The formulations are prepared in a known manner, for example
by extending the active compound with solvents and/or carriers, if
desired using emulsifiers and dispersants. Solvents/auxiliaries
which are suitable for this purpose are essentially: [0130] water,
aromatic solvents (for example Solvesso products, xylene),
paraffins (for example mineral oil fractions), alcohols (for
example methanol, butanol, pentanol, benzyl alcohol), ketones (for
example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP,
NOP), acetates (glycol diacetate), glycols, fatty acid
dimethylamides, fatty acids and fatty acid esters. In principle,
solvent mixtures may also be used, [0131] carriers such as ground
natural minerals (for example kaolins, clays, talc, chalk) and
ground synthetic minerals (for example finely divided silica,
silicates); emulsifiers such as nonionic and anionic emulsifiers
(for example polyoxyethylene fatty alcohol ethers, alkylsulfonates
and arylsulfonates) and dispersants such as lignosulfite waste
liquors and methylcellulose.
[0132] Suitable surfactants are alkali metal, alkaline earth metal
and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid,
phenolsulfonic acid, dibutylnaphthalenesulfonic acid,
alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol
sulfates, fatty acids and sulfated fatty alcohol glycol ethers,
furthermore condensates of sulfonated naphthalene and naphthalene
derivatives with formaldehyde, condensates of naphthalene or of
naphthalenesulfonic acid with phenol and formaldehyde,
polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol,
octylphenol, nonylphenol, alkylphenyl polyglycol ethers,
tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether,
alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene
oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol
ether acetal, sorbitol esters, lignosulfite waste liquors and
methylcellulose.
[0133] Substances which are suitable for the preparation of
directly sprayable solutions, emulsions, pastes or oil dispersions
are mineral oil fractions of medium to high boiling point, such as
kerosene or diesel oil, furthermore coal tar oils and oils of
vegetable or animal origin, aliphatic, cyclic and aromatic
hydrocarbons, for example toluene, xylene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes or their derivatives,
methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone,
isophorone, strongly polar solvents, for example dimethyl
sulfoxide, N-methylpyrrolidone and water.
[0134] Powders, materials for broadcasting and dustable products
can be prepared by mixing or concomitantly grinding the active
substances with a solid carrier.
[0135] Granules, for example coated granules, impregnated granules
and homogeneous granules, can be prepared by binding the active
compounds to solid carriers. Examples of solid carriers are mineral
earths such as silica gels, silicates, talc, kaolin, attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous
earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground
synthetic materials, fertilizers, such as, for example, ammonium
sulfate, ammonium phosphate, ammonium nitrate, ureas, and products
of vegetable origin, such as cereal meal, tree bark meal, wood meal
and nutshell meal, cellulose powders and other solid carriers.
[0136] In general, the formulations comprise from 0.01 to 95% by
weight, preferably from 0.1 to 90% by weight, of the active
compound. The active compounds are employed in a purity of from 90%
to 100%, preferably 95% to 100% (according to NMR spectrum).
[0137] The following are examples of formulations: 1. Products for
dilution with water
A Water-Soluble Concentrates (SL, LS)
[0138] 10 parts by weight of the active compounds are dissolved in
90 parts by weight of water or in a water-soluble solvent. As an
alternative, wetting agents or other auxiliaries are added. The
active compound dissolves upon dilution with water. In this way, a
formulation having a content of 10% by weight of active compound is
obtained.
B Dispersible Concentrates (DC)
[0139] 20 parts by weight of the active compounds are dissolved in
70 parts by weight of cyclohexanone with addition of 10 parts by
weight of a dispersant, for example polyvinylpyrrolidone. Dilution
with water gives a dispersion. The active compound content is 20%
by weight
C Emulsifiable Concentrates (EC)
[0140] 15 parts by weight of the active compounds are dissolved in
75 parts by weight of xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5
parts by weight). Dilution with water gives an emulsion. The
formulation has an active compound content of 15% by weight.
D Emulsions (EW, EO, ES)
[0141] 25 parts by weight of the active compounds are dissolved in
35 parts by weight of xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5
parts by weight). This mixture is introduced into 30 parts by
weight of water by means of an emulsifying machine (e.g.
Ultraturrax) and made into a homogeneous emulsion. Dilution with
water gives an emulsion. The formulation has an active compound
content of 25% by weight.
E Suspensions (SC, OD, FS)
[0142] In an agitated ball mill, 20 parts by weight of the active
compounds are comminuted with addition of 10 parts by weight of
dispersants and wetting agents and 70 parts by weight of water or
an organic solvent to give a fine active compound suspension.
Dilution with water gives a stable suspension of the active
compound. The active compound content in the formulation is 20% by
weight.
F Water-Dispersible Granules and Water-Soluble Granules (WG,
SG)
[0143] 50 parts by weight of the active compounds are ground finely
with addition of 50 parts by weight of dispersants and wetting
agents and prepared as water-dispersible or water-soluble granules
by means of technical appliances (for example extrusion, spray
tower, fluidized bed). Dilution with water gives a stable
dispersion or solution of the active compound. The formulation has
an active compound content of 50% by weight.
G Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS,
WS)
[0144] 75 parts by weight of the active compounds are ground in a
rotor-stator mill with addition of 25 parts by weight of
dispersants, wetting agents and silica gel. Dilution with water
gives a stable dispersion or solution of the active compound. The
active compound content of the formulation is 75% by weight.
H Gel Formulations (GF)
[0145] In a ball mill, 20 parts by weight of the active compounds,
10 parts by weight of dispersant, 1 part by weight of gelling agent
and 70 parts by weight of water or an organic solvent are ground to
give a fine suspension. On dilution with water, a stable suspension
having an active compound content of 20% by weight is obtained.
2. Products to be Applied Undiluted
I Dustable Powders (DP, DS)
[0146] 5 parts by weight of the active compounds are ground finely
and mixed intimately with 95 parts by weight of finely divided
kaolin. This gives a dustable product having an active compound
content of 5% by weight.
J Granules (GR, FG, GG, MG)
[0147] 0.5 part by weight of the active compounds is ground finely
and associated with 99.5 parts by weight of carriers. Current
methods are extrusion, spray-drying and the fluidized bed. This
gives granules to be applied undiluted having an active compound
content of 0.5% by weight.
K ULV Solutions (UL)
[0148] 10 parts by weight of the active compounds are dissolved in
90 parts by weight of an organic solvent, for example xylene. This
gives a product to be applied undiluted having an active compound
content of 10% by weight.
[0149] For seed treatment, use is usually made of water-soluble
concentrates (LS), suspensions (FS), dustable powders (DS),
water-dispersible and water-soluble powders (WS, SS), emulsions
(ES), emulsifiable concentrates (EC) and gel formulations (GF).
These formulations can be applied to the seed in undiluted form or,
preferably, diluted. Application can be carried out prior to
sowing.
[0150] The active compounds can be used as such, in the form of
their formulations or of the use forms prepared therefrom, e.g. in
the form of directly sprayable solutions, powders, suspensions or
dispersions, emulsions, oil dispersions, pastes, dustable products,
materials for broadcasting or granules, by means of spraying,
atomizing, dusting, broadcasting or watering. The use forms depend
entirely on the intended purposes; they should always ensure the
finest possible distribution of the active compounds according to
the invention.
[0151] Aqueous use forms can be prepared from emulsion
concentrates, pastes or wettable powders (spray powders, oil
dispersions) by addition of water. To prepare emulsions, pastes or
oil dispersions, the substances can be homogenized in water, as
such or dissolved in an oil or solvent, by means of wetting agents,
tackifiers, dispersants or emulsifiers. However, it is also
possible to prepare concentrates comprising active substance,
wetting agent, tackifier, dispersant or emulsifier and possibly
solvent or oil which are suitable for dilution with water.
[0152] The concentrations of active compound in the ready-for-use
preparations can be varied within relatively wide ranges. In
general, they are between 0.0001 and 10%, preferably between 0.01
and 1%.
[0153] The active compounds can also be used with great success in
the ultra-low volume (ULV) process, it being possible to apply
formulations with more than 95% by weight of active compound or
even the active compound without additives.
[0154] Oils of various types, wetting agents, adjuvants,
herbicides, fungicides, other pesticides and bactericides can be
added to the active compounds, if appropriate also not until
immediately before use (tank mix). These agents can be added to the
preparations according to the invention in a weight ratio of 1:100
to 100:1, preferably of 1:10 to 10:1.
[0155] Suitable adjuvants in this sense are in particular:
organically modified polysiloxanes, for example Break Thru S
240.RTM.; alcohol alkoxylates, for example Atplus 245.RTM., Atplus
MBA 1303.RTM., Plurafac LF 300.RTM. and Lutensol ON 30.RTM.; EO/PO
block polymers, for example Pluronic RPE 2035.RTM. and Genapol
B.RTM.; alcohol ethoxylates, for example Lutensol XP 80.RTM.; and
sodium dioctylsulfosuccinate, for example Leophen RA.RTM..
[0156] The compositions according to the invention can, in the use
form as fungicides, also be present together with other active
compounds, e.g. with herbicides, insecticides, growth regulators,
fungicides or also with fertilizers. When mixing the compounds (I)
or the compositions comprising them with one or more further active
compounds, in particular fungicides, it is in many cases possible
to widen the activity spectrum or to prevent the development of
resistance. In many cases, synergistic effects are obtained.
[0157] The following list of fungicides, with which the compounds
according to the invention can be used in conjunction, is intended
to illustrate the possible combinations but does not limit
them:
Strobilurins
[0158] azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin,
kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin,
trifloxystrobin, orysastrobin, methyl
(2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate,
methyl
(2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate,
methyl
2-(ortho-(2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate-
;
Carboxamides
[0159] carboxanilides: benalaxyl, benodanil, boscalid, carboxin,
mepronil, fenfuram, fenhexamid, flutolanil, furametpyr, metalaxyl,
ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide,
tiadinil,
N-(4'-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide-
,
N-(4'-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5--
carboxamide,
N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5--
carboxamide,
N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazol-
e-4-carboxamide,
N-(2-cyanophenyl)-3,4-dichloroisothiazole-5-carboxamide; [0160]
carboxylic acid morpholides: dimethomorph, flumorph; [0161]
benzamides: flumetover, fluopicolide (picobenzamid), zoxamide;
[0162] other carboxamides: carpropamid, diclocymet, mandipropamid,
N-(2-(4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl)ethyl)-2-metha-
nesulfonylamino-3-methylbutyramide,
N-(2-(4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl)ethyl)-2-ethan-
esulfonylamino-3-methylbutyramide;
Azoles
[0162] [0163] triazoles: bitertanol, bromuconazole, cyproconazole,
difenoconazole, diniconazole, enilconazole, epoxiconazole,
fenbuconazole, flusilazole, fluquinconazole, flutriafol,
hexaconazole, imibenconazole, ipconazole, metconazole,
myclobutanil, penconazole, propiconazole, prothioconazole,
simeconazole, tebuconazole, tetraconazole, triadimenol,
triadimefon, triticonazole; [0164] imidazoles: cyazofamid,
imazalil, pefurazoate, prochloraz, triflumizole; [0165]
benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
[0166] others: ethaboxam, etridiazole, hymexazole;
Nitrogenous Heterocyclyl Compounds
[0166] [0167] pyridines: fluazinam, pyrifenox,
3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]-pyridine;
[0168] pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol,
mepanipyrim, nuarimol, pyrimethanil; [0169] piperazines: triforine;
[0170] pyrroles: fludioxonil, fenpiclonil; [0171] morpholines:
aldimorph, dodemorph, fenpropimorph, tridemorph; [0172]
dicarboximides: iprodione, procymidone, vinclozolin; [0173] others:
acibenzolar-5-methyl, anilazine, captan, captafol, dazomet,
diclomezine, fenoxanil, folpet, fenpropidin, famoxadone,
fenamidone, octhilinone, probenazole, proquinazid, pyroquilon,
quinoxyfen, tricyclazole,
5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tria-
zolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-3-propylchromen-4-one,
N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4]triazo-
le-1-sulfonamide;
Carbamates and Dithiocarbamates
[0173] [0174] dithiocarbamates: ferbam, mancozeb, maneb, metiram,
metam, propineb, thiram, zineb, ziram; [0175] carbamates:
diethofencarb, flubenthiavalicarb, iprovalicarb, propamocarb,
methyl
3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)prop-
ionate, 4-fluorophenyl
N-(1-(1-(4-cyanophenyl)ethanesulfonyl)but-2-yl)carbamate;
Other Fungicides
[0175] [0176] guanidines: dodine, iminoctadine, guazatine; [0177]
antibiotics: kasugamycin, polyoxins, streptomycin, validamycin A;
[0178] organometallic compounds: fentin salts; [0179]
sulfur-containing heterocyclyl compounds: isoprothiolane,
dithianon; [0180] organophosphorus compounds: edifenphos, fosetyl,
fosetyl-aluminum, iprobenfos, pyrazophos, tolclofos-methyl,
phosphorous acid and its salts; [0181] organochlorine compounds:
thiophanate-methyl, chlorothalonil, dichlofluanid, tolylfluanid,
flusulfamide, phthalide, hexachlorobenzene, pencycuron, quintozene;
[0182] nitrophenyl derivatives: binapacryl, dinocap, dinobuton;
[0183] inorganic active compounds: Bordeaux mixture, copper
acetate, copper hydroxide, copper oxychloride, basic copper
sulfate, sulfur; [0184] others: spiroxamine, cyflufenamid,
cymoxanil, metrafenone.
SYNTHESIS EXAMPLES
[0185] The procedure described in the following synthesis example
was used to prepare further compounds I by appropriate modification
of the starting materials. The compounds obtained in this manner
are listed in the table below, together with physical data.
Example 1
Preparation of
(4-chlorophenyl)-[5-(2,5-difluorophenyl)-5-hydroxy-3-trifluoromethyl-4,5--
dihydropyrazol-1-yl]methanone [1-6]
[0186] A solution of 0.68 g of 4-chlorobenzoic acid hydrazide and
1.01 g of 1-(2,5-difluorophenyl)-4,4,4-trifluoro-1,3-butanedione in
20 ml of ethanol was stirred at 80.degree. C. for 8 hours. The
reaction mixture was freed from the solvent and purified by
chromatography on silica gel. This gave 0.30 g of the title
compound as colorless crystals of melting point 110-113.degree.
C.
Example 2
Preparation of
(3-aminophenyl)-[5-(4-chloro-2,5-difluorophenyl)-5-hydroxy-3-trifluoromet-
hyl-4,5-dihydropyrazol-1-yl]methanone [1-18]
[0187] A solution of 0.61 g of 3-aminobenzoic acid hydrazide and
1.15 g of
1-(4-chloro-2,5-difluorophenyl)-4,4,4-trifluoro-1,3-butanedione in
20 ml of ethanol was stirred at 80.degree. C. for 8 hours. The
reaction mixture was freed from the solvent and purified by
chromatography on silica gel. This gave 0.33 g of the title
compound as colorless crystals of melting point 123-124.degree.
C.
TABLE-US-00002 TABLE I Phys. Data (m.p. [.degree. C.]; No. L.sup.1
L.sup.2 L.sup.3 L.sup.4 L.sup.5 X R.sup.1.sub.m R.sup.2 R.sup.3
R.sup.4 .sup.1H-NMR (CDCl.sub.3 .delta. [ppm]) I-1 H H H CH.sub.3 H
O 2,4-F.sub.2 H H CF.sub.3 163-166 I-2 H H H Br H O 2,4-F.sub.2 H H
CF.sub.3 134-136 I-3 H H H Cl H O 2,4-F.sub.2 H H CF.sub.3 7.7 (m);
7.4 (m); 6.9 (m); 6.75 (m); 5.5 (s); 3.4 (m) I-4 H H H CH.sub.3 H O
2,5-F.sub.2 H H CF.sub.3 7.75 (d); 7.45 (m); 7.2 (d); 7.0 (m); 5.6
(s); 3.2 (m); 2.2 (s) I-5 H H H Br H O 2,5-F.sub.2 H H CF.sub.3 7.7
(d); 7.55 (d); 7.45 (m); 7.05 (m); 5.5 (s); 3.2 (m) I-6 H H H Cl H
O 2,5-F.sub.2 H H CF.sub.3 110-113 I-7 H H CH.sub.3 H H O
2,5-F.sub.2 H H CF.sub.3 115-118 I-8 H H Cl H H O 2,5-F.sub.2 H H
CF.sub.3 7.8 (s); 7.75 (d); 7.45 (m); 7.3 (m); 7.0 (m); 5.5 (s);
3.4 (m) I-9 H H CH.sub.3 H H O 2,4-F.sub.2 H H CF.sub.3 163-165
I-10 H H Cl H H O 2,4-F.sub.2 H H CF.sub.3 130-133 1-11 H Cl H H H
O 2,4-F.sub.2 H H CF.sub.3 7.7 (m); 7.4 (m); 6.95 (m); 5.25 (s);
3.2 (m) 1-12 H Cl H Cl H O 2,4-F.sub.2 H H CF.sub.3 7.7 (m); 7.45
(s); 7.2 (m); 6.9 (m); 5.4 (s); 3.45 (m) 1-13 H Cl H Cl H O
2,5-F.sub.2 H H CF.sub.3 7.5 (m); 7.25 (m); 7.1 (m); 5.2 (s); 3.45
(m) 1-14 H CF.sub.3 H F H O 2,5-F.sub.2 H H CF.sub.3 7.45 (m); 7.25
(m); 7.05 (m); 5.05 (s); 3.3 (m) 1-15 H H H Cl H O 5-Cl,
2,5-F.sub.2 H H CF.sub.3 164-166 1-16 H H H Cl H O 2-F, 4-Cl,
5-OCH.sub.3 H H CF.sub.3 210-213 1-17 H H Cl H H O 5-Cl,
2,5-F.sub.2 H H CF.sub.3 145-147 1-18 H H NH.sub.2 H H O 5-Cl,
2,5-F.sub.2 H H CF.sub.3 123-124 1-19 H H CH.sub.3 H H O
3-CH.sub.3, 4-Cl H H CF.sub.3 7.8 (m); 7.45 (s); 7.35 (m); 6.7 (s);
3.6 (m); 2.45 (s); 2.35 (s) 1-20 H H Cl H H O 3-CH.sub.3, 4-Cl H H
CF.sub.3 8.0 (s); 7.9 (d); 7.4 (m); 6.55 (s); 3.6 (m); 2.4 (s) 1-21
H Cl H Cl H O 3-CH.sub.3, 4-Cl H H CF.sub.3 122-123 1-22 H Cl H H H
O 5-Cl, 2,5-F.sub.2 H H CF.sub.3 7.7 (m); 7.6 (m); 7.4 (m); 7.2
(m); 5.5 (s); 3.45 (m)
Examples of the Action Against Harmful Fungi
[0188] The fungicidal action of the compounds of the formula I was
demonstrated by the following tests:
[0189] The active compounds were prepared as a stock solution
comprising 25 mg of active compound which was made up to 10 ml
using a mixture of acetone and/or DMSO and the emulsifier
Uniperol.RTM. EL (wetting agent having emulsifying and dispersing
action based on ethoxylated alkylphenols) in a volume ratio of
solvent/emulsifier of 99 to 1. The mixture was then made up with
water to 100 ml. This stock solution was diluted with the
solvent/emulsifier/water mixture described to the concentration of
active compounds stated below.
Use Example 1
Curative Activity Against Brown Rust of Wheat Caused by Puccinia
recondita
[0190] Leaves of potted wheat seedlings of the cultivar "Kanzler"
were inoculated with a spore suspension of brown rust (Puccinia
recondita). The pots were then placed in a chamber with high
atmospheric humidity (90 to 95%) and at 20 to 22.degree. C. for 24
hours. During this time, the spores germinated and the germ tubes
penetrated into the leaf tissue. The next day, the infected plants
were sprayed to run-off point with the active compound solution
described above at the active compound concentration stated below.
After the spray coating had dried on, the test plants were
cultivated in a greenhouse at temperatures between 20 and
22.degree. C. and at 65 to 70% relative atmospheric humidity for 7
days. The extent of the rust fungus development on the leaves was
then determined.
[0191] In this test, the plants which had been treated with 250 ppm
of the active compound I-2, I-9 or I-14 showed an infection of not
more than 5%, whereas the untreated plants were 90% infected.
Use Example 2
Curative Activity Against Soybean Rust Caused by Phakopsora
pachyrhizi
[0192] Leaves of potted soybean seedlings of the cultivar "Oxford"
were inoculated with a spore suspension of soybean rust (Phakpsora
pachyrhizi). The pots were then placed into a chamber with high
atmospheric humidity (90 to 95%) and at 23 to 27.degree. C. for 24
hours. During this time, the spores germinated and the germ tubes
penetrated into the leaf tissue. After 1 day, the infected plants
were sprayed to run-off point with the active compound solution
described above at the active compound concentration stated below.
After the spray coating had dried on, the test plants were
cultivated in a greenhouse at temperatures between 23 and
27.degree. C. and at 60 to 80% relative atmospheric humidity for 14
days. The extent of the rust fungus development on the leaves was
then determined.
[0193] In this test, the plants which had been treated with 1000
ppm of the active compound I-17 showed an infection of 3%, whereas
the untreated plants were 90% infected.
* * * * *